EP0456908A1 - Process for activating substrate surfaces for electroless plating - Google Patents
Process for activating substrate surfaces for electroless plating Download PDFInfo
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- EP0456908A1 EP0456908A1 EP90125208A EP90125208A EP0456908A1 EP 0456908 A1 EP0456908 A1 EP 0456908A1 EP 90125208 A EP90125208 A EP 90125208A EP 90125208 A EP90125208 A EP 90125208A EP 0456908 A1 EP0456908 A1 EP 0456908A1
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- EP
- European Patent Office
- Prior art keywords
- weight
- activator
- formulation
- formulation according
- metallized
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
- H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
Definitions
- Preferred spray activator formulations therefore contain a solvent mixture of: 30-60% by weight glycol ether acetates 30-60% by weight of aliphatic ketones 4 - 40 wt .-% aliphatic alcohols.
- glycol ether acetates include reaction products of ethylene glycol or propylene glycol with aliphatic alcohols and acetic acid, such as e.g. Ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate understood.
- aliphatic ketones straight chain, branched or cyclic ketones with 3 to 7 carbon atoms such as e.g. Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone used.
- Aliphatic alcohols include straight-chain or branched alcohols with 2 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, n-butanol and isobutanol, which are optionally substituted by a keto group, such as e.g. Diacetone alcohol.
- Suitable activators in the formulations according to the invention are organometallic compounds of the 1st and 8th subgroups of the periodic table (in particular Pd, Pt, Au, Ag), as are described, for example, in EP-A 34 485, 81 438, 131 198.
- organometallic complex compounds of palladium with olefins (dienes), with ⁇ ⁇ -unsaturated carbonyl compounds, with crown ethers and with nitriles are suitable.
- Bisacetonitrile palladium dichloride, butadiene palladium dichloride, 4-cyclohexane-1,2-dicarboxylic acid anhydride palladium dichloride, mesityl oxide palladium dichloride, 3-hepten-2-one palladium chloride and 5-methyl-3-hexane-2-one palladium chloride are very particularly suitable.
- Auxiliaries known from printing or coating technology such as pigments, disperse silicas, carbon blacks, silicates, rheological additives and clay minerals, are suitable as fillers.
- binders according to the invention are known from polyurethane chemistry. They are made, for example, by reacting polyesters and / or polyethers with aromatic polyisocyanates and a chain extender, e.g. a low molecular weight diol, e.g. Butanediol or neopentyl glycol.
- a chain extender e.g. a low molecular weight diol, e.g. Butanediol or neopentyl glycol.
- Linear, aromatic polyurethane elastomers such as those produced from butanediol polyadipate, neopentyl glycol and 4,4'-diphenylmethane diisocyanate, have proven to be particularly suitable.
- binders can also be used, e.g. Polyacrylate polyols, polyester diols and polyether diols.
- the formulations may contain surfactants, leveling agents, dyes and / or extenders such as Xylene, toluene or n-butyl acetate.
- the formulations according to the invention are generally prepared by mixing the constituents.
- the formulation components can also be incorporated in separate steps.
- the activator can first be placed in a solvent component of the overall formulation, e.g. pre-dissolve or disperse in ketones and then filler, e.g. Add Aerosil®.
- this preparation is stirred into or dispersed in the remaining solvent mixture which contains the binder.
- surfaces can be used for a more adhesive chemical metallization can be activated.
- spraying on the formulations can be replaced by dipping, brushing and rolling up.
- Suitable substrates for the process according to the invention are paper, enamel, ceramics, polyethylene, polypropylene, epoxy resins, polyesters, polycarbonates, polyamides, polyimides, polyhydantoins, ABS plastics, silicones, polyvinyl halides and polyvinylidene fluoride in the form of films, sheets, papers and nonwovens.
- Substrates such as are used as housings in the electronics industry are particularly preferred, e.g. ABS and polycarbonate plastics or their blends, polyphenylene sulfide, polybutylene terephthalate and their blends and polypropylene oxide.
- the solvents are removed. This is done by drying or tempering at substrate-specific temperatures, for example between room temperature and 240 ° C under normal pressure, increased pressure or vacuum. The drying time can be varied.
- the surfaces treated in this way must then be activated by reduction, e.g. through reducing agents such as formaldehyde, hypophosphites, rongalite and boranes.
- reducing agents such as formaldehyde, hypophosphites, rongalite and boranes.
- a preferred embodiment of the method is that the reduction in the metallization bath is the same is carried out with the reducing agent of electroless metallization. This applies, for example, to nickel and copper baths.
- the surfaces treated with the formulations according to the invention can be metallized without current in a further process step.
- the metallization baths that are suitable for this are known in the art of electroless metallization.
- the formulations according to the invention are particularly suitable for the partial activation of geometrically complicated surfaces, in particular for the production of molded bodies metallized on one or both sides or of housing parts metallized on the inside for the electronics industry for the purpose of electromagnetic shielding.
- This method can of course also be used to produce structured metal surfaces using a suitable mask.
- the formulation was prepared by introducing the polyurethane into MPA, adding methyl ethyl ketone and n-butanol, then stirring in bisacetonitrile palladium dichloride and finally stirring in Aerosil® 380.
- the spray activator formulation prepared in this way was sprayed free of stress cracks by means of a spray gun with air support on injection-molded test plates (100 ⁇ 150 mm).
- the spraying distance was approx. 40 cm; the nozzle cross section was 1.5 mm; the air metering (2 to 6 dar) could be varied.
- ABS polymer acrylonitrile-butadiene-styrene copolymer
- polyester of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate substrate.
- the sprayed stress crack free test plates were air dried for 1 hour and then annealed in the drying oven at 70 ° C for 1 hour.
- the copper was deposited evenly. A closed metal surface was created.
- the metallized test plates were removed from the metal bath and rinsed thoroughly with demineralized water and annealed in a drying cabinet for 1 hour.
- test plates were provided with an electrodeposited Cu layer
- the adhesive strength according to DIN 53 494 was: 15 N / 25 mm
- the spray activator formulation was prepared as in Example 1.
- the formulation was sprayed free of stress cracking by means of a spray gun with air support on an injection molded test plate (100 x 150 mm) made of a polycarbonate made of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid, the plate after drying at 100 ° C./1 h annealed for a long time, metallized in a metal bath at 20 ° C / 1 h and then annealed at 100 ° C / 1 h. A coherent metal layer was obtained.
- Adhesive strength according to DIN 53 494 10 N / 25 mm.
- the spray activator formulation was prepared and the process carried out as in Example 1.
- An ABS polymer (acrylonitrile-butadiene-styrene copolymer) was used as the substrate.
- the adhesive strength of the metal pad was 8N / 25 mm.
- the formulation was prepared and carried out as in Example 4.
- a blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate.
- the formulation was prepared and carried out as in Example 4.
- a blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate .
- Adhesive strength according to DIN 53 494 15 N / 25 mm.
- the formulation was sprayed onto test plates made of a polycarbonate composed of 4,4'-dihydroxyphenyl-2,2-propane and carbonic acid, then annealed at 100 ° C./1 h, metallized for 3 h at 20 ° C., rinsed thoroughly with water and 1 h annealed in a drying oven at 100 ° C.
- the chemical Cu layer was all over and without cracks.
- the formulation was sprayed onto polycarbonate test panels made from a polycarbonate of 4,4'-dihydroxyphenyl-2,2-propane and carbonic acid. Then the test plates were annealed at 100 ° C. for 1 hour, metallized for 2 hours at 24 ° C. in a metallization bath and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 100 ° C for 1 h.
- the spray activator formulation was prepared as in Example 8.
- a blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid served as the substrate.
- the mixture was annealed at 70 ° C. for 1 hour, then at 24 ° C. for 2 hours Metallization bath metallized and rinsed thoroughly with water. A coherent metal layer was obtained. The mixture was then heated at 70 ° C for 1 h.
- the formulation was sprayed onto polycarbonate test panels made from a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid.
- the plates were then annealed at 100 ° C. for 1 hour, metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained.
- the mixture was then heated at 100 ° C for 1 h.
- the spray activator formulation was prepared as in Example 10.
- a polymer blend as in Example 9 was used as the substrate. After spraying the formulation onto test plates, the mixture was annealed at 70 ° C. for 1 hour, then metallized at 24 ° C. for 2 hours in a metal plating bath and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 70 ° C for 1 h.
- Calcium carbonate was last added to the formulation, but can also be added elsewhere in the formulation preparation.
- the formulation was sprayed onto polycarbonate test panels as in Example 8. The plates were then annealed at 100 ° C. for 1 hour, metallized in a copper bath at 24 ° C. for 2 hours and rinsed thoroughly with water.
- a metal layer was obtained.
- the mixture was then heated at 100 ° C for 1 h.
- Adhesive strength according to DIN 53 494 10 N / 25 mm.
- the spray activator formulation was prepared as in Example 12.
- a blend of ABS polymer and a polyester as in Example 9 was used as the substrate.
- the mixture was annealed at 70 ° C. for 1 hour, then metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 70 ° C for 1 h.
- Calcium carbonate was last added to the formulation, but can also be added elsewhere in the preparation of the formulation.
- the formulation was sprayed onto polycarbonate test panels as in Example 8. The mixture was then heated at 100 ° C. for 1 hour, metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 100 ° C for 1 h.
- the spray activator formulation was prepared as in Example 14.
- a blend of ABS polymer and a polyester as in Example 9 was used as the substrate.
- the mixture was annealed at 70 ° C. for 1 hour, then metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 70 ° C. for 1 hour.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Chemically Coating (AREA)
Abstract
Description
Es ist allgemein bekannt, daß polymere Werkstoffe vor dem chemischen Metallisieren vorbehandelt werden müssen, z.B. durch Ätzen der Polymeroberfläche mit Chromschwefelsäuren. Dieses Verfahren ist jedoch nur auf solche Polymeren anwendbar, deren Oberfläche sich oxidativ unter Bildung von Kavernen und Vakuolen verändern läßt.It is well known that polymeric materials must be pretreated prior to chemical metallization, e.g. by etching the polymer surface with chromic sulfuric acids. However, this method is only applicable to those polymers whose surface can be changed oxidatively with the formation of caverns and vacuoles.
Ferner ist bekannt, daß das Arbeiten mit Chromschwefelsäure, SO₃-Dampf oder anderen Oxidantien mit einer Verschlechterung der physikalischen Eigenschaften, wie der Kerbschlagzähigkeit und des elektrischen Oberflächenwiderstands des polymeren Werkstoffs, einhergeht. Darüber hinaus stören oftmals Spuren von sechswertigem Chrom, die rasch zu einer Vergiftung der Metallbäder führen.It is also known that working with chromosulfuric acid, SO₃ steam or other oxidants is accompanied by a deterioration in the physical properties, such as the impact strength and the electrical surface resistance of the polymeric material. In addition, traces of hexavalent chromium often interfere, which quickly lead to poisoning of the metal baths.
Die bekannten Verfahren zur stromlosen Metallisierung von Werkstoffen bestehen im übrigen aus mehreren Verfahrensstufen und haben den Nachteil, daß sie nicht direkt auf alle Polymeren anwendbar sind. Oftmals muß eine chemische oder physikalische Aufrauhung durchgeführt werden.The known methods for electroless metallization of materials also consist of several process steps and have the disadvantage that they cannot be used directly on all polymers. Often must chemical or physical roughening can be carried out.
Es ist deshalb bereits vorgeschlagen worden, die Polymeroberflächen sehr schonend mit metallorganischen Katalysatoren zu aktivieren (vgl. z.B. US-A 3 560 257 und EP-A 81 129). Diese an sich sehr elegante Methode ist indessen ebenfalls nicht universell anwendbar. Darüber hinaus führt der Einsatz von Lösungsmitteln häufig zur Auslösung der Spannungsrißkorrosion des unter Zug- oder Druckspannung stehenden Polymerspritzgußteiles.It has therefore already been proposed to activate the polymer surfaces very gently with organometallic catalysts (see, for example, US Pat. No. 3,560,257 and EP-A 81 129). However, this method, which is very elegant in itself, is also not universally applicable. In addition, the use of solvents often leads to the initiation of stress corrosion cracking of the polymer injection molded part under tension or compression.
Andere Verfahren, wie sie in US-A 3 560 257 und 4 017 265 sowie DE-A 3 627 256 beschrieben werden, haben den Nachteil, daß sie relativ größere Mengen an teuren Edelmetallaktivatoren erfordern,Other processes, as are described in US Pat. Nos. 3,560,257 and 4,017,265 and DE-A 3,627,225, have the disadvantage that they require relatively large amounts of expensive noble metal activators,
Es wurde nun überraschenderweise gefunden, daß man ohne die genannten Nachteile, insbesondere unter Vermeidung der Spannungsrißkorrosion, gut haftende Metallschichten auf Kunststoffoberflächen erzeugen kann, wenn man diese ohne vorheriges Beizen mit einer Aktivatorformulierung auf der Basis von organischen Edelmetallverbindungen, Füllstoffen, organischen Lösungsmittelgemischen und Polyurethanelastomeren als Bindemittel behandelt, wobei als Lösungsmittelgemisch ein Gemisch aus Glykoletheracetaten, aliphatischen Ketonen und aliphatischen Alkoholen verwendet wird.It has now surprisingly been found that, without the disadvantages mentioned, in particular while avoiding stress corrosion cracking, metal layers which adhere well to plastic surfaces can be produced if they are treated without prior pickling with an activator formulation based on organic noble metal compounds, fillers, organic solvent mixtures and polyurethane elastomers Treated binders, a mixture of glycol ether acetates, aliphatic ketones and aliphatic alcohols being used as the solvent mixture.
Bevorzugte Formulierungen enthalten:
- a) 0,03 bis 3,0 Gew.-%
- einer organischen Edelmetallverbindung als Aktivator,
- b) 20 bis 60 Gew.-%
- Glykoletheracetate,
- c) 20 bis 60 Gew.-%
- aliphatische Ketone,
- d) 4 bis 60 Gew.-%
- aliphatische Alkohole,
- e) 0,5 bis 3,0 Gew.-%
- Füllstoffe,
- f) 4 bis 20 Gew.-%
- Polyurethanelastomere als Bindemittel,
- a) 0.03 to 3.0% by weight
- an organic precious metal compound as an activator,
- b) 20 to 60% by weight
- Glycol ether acetates,
- c) 20 to 60% by weight
- aliphatic ketones,
- d) 4 to 60% by weight
- aliphatic alcohols,
- e) 0.5 to 3.0% by weight
- Fillers,
- f) 4 to 20% by weight
- Polyurethane elastomers as binders,
Nach der Aktivierung wird in üblicher Weise metallisiert.After activation, metallization is carried out in the usual way.
Es ist überraschend, daß die erfindungsgemäßen Formulierungen Spannungsrißkorrosion auf verschiedenen Kunststoffen vermeiden und gleichzeitig eine haftfeste Metallisierung bewirken, da auf Oberflächen, die nur mit einem Lösungsmittel behandelt worden sind, entweder sofortige Rißbildung im Kunststoff auftritt oder die Rißbildung bei lösungsmittelempfindlichen Kunststoffen zwar ausbleibt, dafür aber keine haftfeste bzw. eine ungleichmäßige Metallisierung aufgrund einer nicht gleichmäßigen Filmbildung erfolgt.It is surprising that the formulations according to the invention avoid stress corrosion cracking on different plastics and at the same time bring about an adherent metallization, since on surfaces that have only been treated with a solvent either immediate crack formation occurs in the plastic or the crack formation does not occur with solvent-sensitive plastics, but it does no adherent or uneven metallization due to non-uniform film formation.
Bevorzugte Sprühaktivatorformulierungen enthalten deshalb ein Lösungsmittelgemisch aus:
30 - 60 Gew.-% Glykoletheracetaten
30 - 60 Gew.-% aliphatischen Ketonen
4 - 40 Gew.-% aliphatischen Alkoholen.Preferred spray activator formulations therefore contain a solvent mixture of:
30-60% by weight glycol ether acetates
30-60% by weight of aliphatic ketones
4 - 40 wt .-% aliphatic alcohols.
Unter Glykoletheracetaten werden im Sinne der Erfindung Umsetzungsprodukte von Ethylenglykol bzw. Propylenglykol mit aliphatischen Alkoholen und Essigsäure, wie z.B. Ethylenglykolethyletheracetat, Propylenglykolmethyletheracetat und Propylenglykolethyletheracetat verstanden.In the context of the invention, glycol ether acetates include reaction products of ethylene glycol or propylene glycol with aliphatic alcohols and acetic acid, such as e.g. Ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate understood.
Als bevorzugte aliphatische Ketone werden gradkettige, verzweigte oder cyclische Ketone mit 3 bis 7 Kohlenstoffatomen wie z.B. Methylethylketon, Methylisobutylketon oder Cyclohexanon, eingesetzt.As preferred aliphatic ketones straight chain, branched or cyclic ketones with 3 to 7 carbon atoms such as e.g. Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone used.
Als aliphatische Alkohole kommen gradkettige oder verzweigte Alkohole mit 2 bis 8 Kohlenstoffatomen wie Ethanol, n-Propanol, Isopropanol, n-Butanol und Isobutanol, die gegebenenfalls durch eine Ketogruppe substituiert sind, wie z.B. Diacetonalkohol, in Betracht.Aliphatic alcohols include straight-chain or branched alcohols with 2 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, n-butanol and isobutanol, which are optionally substituted by a keto group, such as e.g. Diacetone alcohol.
Als Aktivatoren kommen in den erfindungsgemäßen Formulierungen organometallische Verbindungen der 1. und 8. Nebengruppen des Periodensystems (insbesondere Pd, Pt, Au, Ag) in Betracht, wie sie beispielsweise in den EP-A 34 485, 81 438, 131 198 beschrieben werden. Besonders geeignet sind organometallische Komplex-Verbindungen des Palladiums mit Olefinen (Dienen), mit α β-ungesättigten Carbonylverbindungen, mit Kronenethern und mit Nitrilen. Ganz besonders geeignet sind Bisacetonitrilpalladiumdichlorid, Butadienpalladiumdichlorid, 4-Cyclohexan-1,2-dicarbonsäureanhydridpalladiumdichlorid, Mesityloxidpalladiumdichlorid, 3-Hepten-2-on-palladiumchlorid und 5-Methyl-3-hexan-2-on-palladiumchlorid.Suitable activators in the formulations according to the invention are organometallic compounds of the 1st and 8th subgroups of the periodic table (in particular Pd, Pt, Au, Ag), as are described, for example, in EP-A 34 485, 81 438, 131 198. Especially organometallic complex compounds of palladium with olefins (dienes), with α β-unsaturated carbonyl compounds, with crown ethers and with nitriles are suitable. Bisacetonitrile palladium dichloride, butadiene palladium dichloride, 4-cyclohexane-1,2-dicarboxylic acid anhydride palladium dichloride, mesityl oxide palladium dichloride, 3-hepten-2-one palladium chloride and 5-methyl-3-hexane-2-one palladium chloride are very particularly suitable.
Es können auch Gemische dieser Verbindungen eingesetzt werden.Mixtures of these compounds can also be used.
Als Füllstoffe kommen aus der Druck- bzw. Lackierungstechnik bekannte Hilfsstoffe wie Pigmente, disperse Kieselsäuren, Ruße, Silikate, rheologische Additive und Tonmineralien in Betracht.Auxiliaries known from printing or coating technology, such as pigments, disperse silicas, carbon blacks, silicates, rheological additives and clay minerals, are suitable as fillers.
Die erfindungsgemäßen Bindemittel sind aus der Polyurethanchemie bekannt. Sie werden beispielsweise hergestellt durch Umsetzung von Polyestern und/oder Polyethern mit aromatischen Polyisocyanaten und einem Kettenverlängerer, z.B. einem niedermolekularen Diol, wie z.B. Butandiol oder Neopentylglykol.The binders according to the invention are known from polyurethane chemistry. They are made, for example, by reacting polyesters and / or polyethers with aromatic polyisocyanates and a chain extender, e.g. a low molecular weight diol, e.g. Butanediol or neopentyl glycol.
Zur Herstellung einer lagerstabilen, versprühbaren und toxikologisch unbedenklichen Formulierung ist es vorteilhaft, Polyurethane einzusetzen, die keine freien Isocyanatgruppen mehr enthalten.To produce a storage-stable, sprayable and toxicologically harmless formulation, it is advantageous to use polyurethanes which no longer contain free isocyanate groups.
Als besonders geeignet haben sich lineare, aromatische Polyurethanelastomere erwiesen, wie sie beispielsweise aus Butandiolpolyadipat, Neopentylglykol und 4,4'-Diphenylmethandiisocyanat hergestellt werden.Linear, aromatic polyurethane elastomers, such as those produced from butanediol polyadipate, neopentyl glycol and 4,4'-diphenylmethane diisocyanate, have proven to be particularly suitable.
Es können auch andere Bindemittel eingesetzt werden, wie z.B. Polyacrylatpolyole, Polyesterdiole und Polyetherdiole.Other binders can also be used, e.g. Polyacrylate polyols, polyester diols and polyether diols.
Neben den Aktivatoren, Füllstoffen, Bindemitteln und Lösungsmittelgemischen enthalten die Formulierungen gegebenenfalls Tenside, Verlaufsmittel, Farbstoffe und/oder Verschnittmittel wie z.B. Xylol, Toluol oder n-Butylacetat.In addition to the activators, fillers, binders and solvent mixtures, the formulations may contain surfactants, leveling agents, dyes and / or extenders such as Xylene, toluene or n-butyl acetate.
Die Herstellung der erfindungsgemäßen Formulierungen geschieht im allgemeinen durch Vermischen der Bestandteile. Das Einarbeiten der Formulierungskomponenten kann auch in getrennten Schritten durchgeführt werden. Beispielsweise kann man den Aktivator zuerst in einer Lösungsmittelkomponente der Gesamtformulierung, z.B. in Ketonen vorlösen bzw. dispergieren und anschließend den Füllstoff, z.B. Aerosil® zugeben.The formulations according to the invention are generally prepared by mixing the constituents. The formulation components can also be incorporated in separate steps. For example, the activator can first be placed in a solvent component of the overall formulation, e.g. pre-dissolve or disperse in ketones and then filler, e.g. Add Aerosil®.
In einem zweiten Schritt wird diese Zubereitung in das restliche Lösungsmittelgemisch, welches das Bindemittel enthält, eingerührt oder dispergiert.In a second step, this preparation is stirred into or dispersed in the remaining solvent mixture which contains the binder.
Vorzugsweise durch Aufsprühen der erfindungsgemäßen Formulierungen mittels aus der Lackindustrie bekannten Verfahren können Oberflächen zum Zwecke einer haftfesten chemischen Metallisierung aktiviert werden. Selbstverständlich kann das Aufsprühen der Formulierungen durch Tauchen, Aufpinseln und Aufrollen ersetzt werden.Preferably by spraying on the formulations according to the invention by means of processes known from the paint industry, surfaces can be used for a more adhesive chemical metallization can be activated. Of course, spraying on the formulations can be replaced by dipping, brushing and rolling up.
Als Substrate für das erfindungsgemäße Verfahren eignen sich Papier, Emaille, Keramik, Polyethylen, Polypropylen, Epoxidharze, Polyester, Polycarbonate, Polyamide, Polyimide, Polyhydantoine, ABS-Kunststoffe, Silikone, Polyvinylhalogenide und Polyvinylidenfluorid in Form von Folien, Platten, Papieren und Vliesen. Besonders bevorzugt sind Substrate, wie sie in der Elektronikindustrie als Gehäuse eingesetzt werden, z.B. ABS-und Polycarbonat-Kunststoffe bzw. deren Blends, Polyphenylensulfid, Polybutylenterephthalat und deren Blends und Polypropylenoxid.Suitable substrates for the process according to the invention are paper, enamel, ceramics, polyethylene, polypropylene, epoxy resins, polyesters, polycarbonates, polyamides, polyimides, polyhydantoins, ABS plastics, silicones, polyvinyl halides and polyvinylidene fluoride in the form of films, sheets, papers and nonwovens. Substrates such as are used as housings in the electronics industry are particularly preferred, e.g. ABS and polycarbonate plastics or their blends, polyphenylene sulfide, polybutylene terephthalate and their blends and polypropylene oxide.
Nach dem Aufbringen der erfindungsgemäßen Formulierungen auf die Oberfläche, z.B. die Innenseite eines Gehäuses, werden die Lösungsmittel entfernt. Dies geschieht durch Trocknen oder Tempern bei substratspezifischen Temperaturen, beispielsweise zwischen Raumtemperatur und 240°C unter Normaldruck, erhöhtem Druck oder Vakuum. Die Trocknungszeit kann dabei variiert werden.After the formulations according to the invention have been applied to the surface, e.g. the inside of a case, the solvents are removed. This is done by drying or tempering at substrate-specific temperatures, for example between room temperature and 240 ° C under normal pressure, increased pressure or vacuum. The drying time can be varied.
Die so behandelten Oberflächen müssen anschließend durch Reduktion aktiviert werden, z.B. durch Reduktionsmittel wie Formaldehyd, Hypophosphite, Rongalit und Borane.The surfaces treated in this way must then be activated by reduction, e.g. through reducing agents such as formaldehyde, hypophosphites, rongalite and boranes.
Eine bevorzugt ausgeführte Form des Verfahrens besteht darin, daß die Reduktion im Metallisierungsbad gleich mit dem Reduktionsmittel der stromlosen Metallisierung durchgeführt wird. Dies gilt beispielsweise für Nickel- und Kupferbäder.A preferred embodiment of the method is that the reduction in the metallization bath is the same is carried out with the reducing agent of electroless metallization. This applies, for example, to nickel and copper baths.
Die mit den erfindungsgemäßen Formulierungen behandelten Oberflächen können in einem weiteren Verfahrensschritt stromlos metallisiert werden. Die dafür in Frage kommenden Metallisierungsbäder sind in der Technik der stromlosen Metallisierung bekannt.The surfaces treated with the formulations according to the invention can be metallized without current in a further process step. The metallization baths that are suitable for this are known in the art of electroless metallization.
Die erfindungsgemäßen Formulierungen eignen sich besonders für die partielle Aktivierung geometrisch komplizierter Oberflächen, besonders zur Herstellung von ein- oder beidseitig metallisierten Formkörpern bzw. von innenseitig metallisierten Gehäuseteilen für die Elektronikindustrie zum Zwecke der elektromagnetischen Abschirmung. Durch dieses Verfahren können selbstverständlich auch strukturierte Metallflächen mittels einer geeigneten Maske hergestellt werden.The formulations according to the invention are particularly suitable for the partial activation of geometrically complicated surfaces, in particular for the production of molded bodies metallized on one or both sides or of housing parts metallized on the inside for the electronics industry for the purpose of electromagnetic shielding. This method can of course also be used to produce structured metal surfaces using a suitable mask.
Bei den in den nachfolgenden Beispielen mit dem Buchstaben "®" gekennzeichneten Produkten handelt es sich um eingetragene Warenzeichen.The products marked with the letter "®" in the following examples are registered trademarks.
Aus Butandiolpolyadipat (MG 2000), Neopentylglykol und 4,4'-Diphenylmethan-diisocyanat wurde ein nicht reaktives Polyurethanelastomer hergestellt und in die folgende Aktivatorformulierung eingebracht:
- 0,5 g
- Bisacetonitrilpalladiumdichlorid
- 500 ml
- Methoxypropylacetat (MPA)
- 450 ml
- Methylethylketon (MEK)
- 50 ml
- n-Butanol
- 23 g
- Aerosil® 380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 0.5 g
- Bisacetonitrile palladium dichloride
- 500 ml
- Methoxypropyl acetate (MPA)
- 450 ml
- Methyl ethyl ketone (MEK)
- 50 ml
- n-butanol
- 23 g
- Aerosil® 380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die Herstellung der Formulierung erfolgte so, daß das Polyurethan in MPA vorgelegt wurde, Methylethylketon und n-Butanol zugefügt, dann Bisacetonitrilpalladiumdichlorid eingerührt und zuletzt Aerosil® 380 eingerührt wurde.The formulation was prepared by introducing the polyurethane into MPA, adding methyl ethyl ketone and n-butanol, then stirring in bisacetonitrile palladium dichloride and finally stirring in Aerosil® 380.
Die so hergestellte Sprühaktivatorformulierung wurde mittels einer Sprühpistole mit Luftunterstützung auf spritzgegossenen Testplatten (100 x 150 mm) Spannungsrißfrei versprüht. Der Spritzabstand betrug ca. 40 cm; der Düsenquerschnitt betrug 1,5 mm; die Luftzudosierung (2 bis 6 Dar) konnte variiert werden.The spray activator formulation prepared in this way was sprayed free of stress cracks by means of a spray gun with air support on injection-molded test plates (100 × 150 mm). The spraying distance was approx. 40 cm; the nozzle cross section was 1.5 mm; the air metering (2 to 6 dar) could be varied.
Als Testplattensubstrat wurde ein Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polyester aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure eingesetzt.A blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polyester of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate substrate.
Die besprühten spannungsrißfreien Testplatten wurden 1 h lang an der Luft getrocknet und dann 1 h im Trockenofen bei 70°C getempert. Die auf Raumtemperatur abgekühlten Testplatten wurden anschließend in ein handelsübliches Cu-Metallisierungsbad mit folgenden Konzentrationen: Cu=3,3 g/l; Natriumhydroxid = 5,4 g/l und Formaldehyd = 9,2 g/l, das auch in dem folgenden Beispiel eingesetzt wurde, 3 h lang bei 20°C getaucht. Die Abscheidung von Kupfer erfolgte gleichmäßig, Es entstand eine geschlossenflächige Metallauflage.The sprayed stress crack free test plates were air dried for 1 hour and then annealed in the drying oven at 70 ° C for 1 hour. The test plates cooled to room temperature were then placed in a commercially available Cu metallization bath with the following concentrations: Cu = 3.3 g / l; Sodium hydroxide = 5.4 g / l and formaldehyde = 9.2 g / l, which was also used in the following example, immersed at 20 ° C. for 3 hours. The copper was deposited evenly. A closed metal surface was created.
Dann wurden die metallisierten Testplatten aus dem Metallbad entfernt und gründlich mit demineralisiertem Wasser abgespült und 1 h lang in einem Trockenschrank getempert.Then the metallized test plates were removed from the metal bath and rinsed thoroughly with demineralized water and annealed in a drying cabinet for 1 hour.
Zur Messung der Haftfestigkeit der Metallschicht nach DIN 53 494 wurden die Testplatten mit einer galvanisch abgeschiedenen Cu-Schicht versehen,To measure the adhesive strength of the metal layer in accordance with DIN 53 494, the test plates were provided with an electrodeposited Cu layer,
Die Haftfestigkeit nach DIN 53 494 betrug: 15 N/25 mmThe adhesive strength according to DIN 53 494 was: 15 N / 25 mm
Die Herstellung der Sprühaktivatorformulierung erfolgte wie in Beispiel 1.The spray activator formulation was prepared as in Example 1.
Die Formulierung wurde mittels einer Spritzpistole mit Luftunterstützung auf einer spritzgegossenen Testplatte (100 x 150 mm) aus einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure spannungsrißfrei versprüht, die Platte nach Abtrocknen bei 100°C/1 h lang getempert, im Metallbad bei 20°C/1 h lang metallisiert und anschließend bei 100°C/1 h lang getempert. Man erhielt eine zusammenhängende Metallschicht.The formulation was sprayed free of stress cracking by means of a spray gun with air support on an injection molded test plate (100 x 150 mm) made of a polycarbonate made of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid, the plate after drying at 100 ° C./1 h annealed for a long time, metallized in a metal bath at 20 ° C / 1 h and then annealed at 100 ° C / 1 h. A coherent metal layer was obtained.
Haftfestigkeit nach DIN 53 494: 10 N/25 mm.Adhesive strength according to DIN 53 494: 10 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung und die Durchführung des Verfahrens erfolgte wie in Beispiel 1. Als Substrat diente ein ABS-Polymerisat (AcrylnitrilButadien-Styrol-Copolymerisat).The spray activator formulation was prepared and the process carried out as in Example 1. An ABS polymer (acrylonitrile-butadiene-styrene copolymer) was used as the substrate.
Die Haftfestigkeit der Metallauflage betrug 8N/25 mm.The adhesive strength of the metal pad was 8N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte wie in Beispiel 1 aus folgenden Komponenten:
- 2,8 g
- Bisacetonitrilpalladiumdichlorid
- 600 ml
- MPA
- 300 ml
- MEK
- 100 ml
- n-Butanol
- 23 g
- Aerosil® 380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 2.8 g
- Bisacetonitrile palladium dichloride
- 600 ml
- MPA
- 300 ml
- MEK
- 100 ml
- n-butanol
- 23 g
- Aerosil® 380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die so hergestellte Formulierung wurde auf einer Testplatte aus einem Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure spannungsrißfrei versprüht, dann bei 70°C/1 h getempert, 3 h bei 20°C in einem stromlosen Cu-Bad behandelt, mit Wasser gründlich gespült und 1 h im Trockenofen bei 70°C getempert.The formulation thus prepared was sprayed on a test plate made of a blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid, free of stress cracks, then at 70 ° C. / Annealed for 1 h, treated in an electroless Cu bath for 3 h at 20 ° C, rinsed thoroughly with water and annealed in a drying oven at 70 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 17 N/25 mm.Adhesive strength according to DIN 53 494: 17 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2,8 g
- Bisacetonitrilpalladiumdichlorid
- 300 ml
- MPA
- 600 ml
- MEK
- 100 ml
- n-Butanol
- 23 g
- Aerosil® 380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 2.8 g
- Bisacetonitrile palladium dichloride
- 300 ml
- MPA
- 600 ml
- MEK
- 100 ml
- n-butanol
- 23 g
- Aerosil® 380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die Herstellung der Formulierung und die Durchführung erfolgte wie im Beispiel 4. Als Testplatte diente ein Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polcarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure.The formulation was prepared and carried out as in Example 4. A blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate.
Haftfestigkeit nach DIN 53 494: 5 N/25 mm.Adhesive strength according to DIN 53 494: 5 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2,8 g
- Bisacetonitrilpalladiumdichlorid
- 600 ml
- MPA
- 300 ml
- MEK
- 100 ml
- Isopropanol
- 23 g
- Aerosil® 380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 2.8 g
- Bisacetonitrile palladium dichloride
- 600 ml
- MPA
- 300 ml
- MEK
- 100 ml
- Isopropanol
- 23 g
- Aerosil® 380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die Herstellung der Formulierung und die Durchführung erfolgte wie im Beispiel 4. Als Testplatte wurde ein Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure eingesetzt.The formulation was prepared and carried out as in Example 4. A blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate .
Haftfestigkeit nach DIN 53 494: 15 N/25 mm.Adhesive strength according to DIN 53 494: 15 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2,8 g
- Bisacetonitrilpalladiumdichlorid
- 300 ml
- MPA
- 600 ml
- MEK
- 100 ml
- n-Butanol
- 23 g
- Aerosil® 380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 2.8 g
- Bisacetonitrile palladium dichloride
- 300 ml
- MPA
- 600 ml
- MEK
- 100 ml
- n-butanol
- 23 g
- Aerosil® 380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die Formulierung wurde auf Testplatten aus einem Polycarbonat aus 4,4'-Dihydroxyphenyl-2,2-propan und Kohlensäure versprüht, dann bei 100°C/1 h getempert, 3 h bei 20°C metallisiert, mit Wasser gründlich gespült und 1 h im Trockenofen bei 100°C getempert. Die chemische Cu-Schicht war ganzflächig und ohne Risse.The formulation was sprayed onto test plates made of a polycarbonate composed of 4,4'-dihydroxyphenyl-2,2-propane and carbonic acid, then annealed at 100 ° C./1 h, metallized for 3 h at 20 ° C., rinsed thoroughly with water and 1 h annealed in a drying oven at 100 ° C. The chemical Cu layer was all over and without cracks.
Haftfestigkeit nach DIN 53 494: 7 N/25 mm.Adhesive strength according to DIN 53 494: 7 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2 g
- Bisacetonitrilpalladiumdichlorid
- 330 ml
- MPA
- 300 ml
- MEK
- 200 ml
- Isopropanol
- 200 ml
- Diacetonalkohol
- 15 g
- Aerosil®380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 2 g
- Bisacetonitrile palladium dichloride
- 330 ml
- MPA
- 300 ml
- MEK
- 200 ml
- Isopropanol
- 200 ml
- Diacetone alcohol
- 15 g
- Aerosil®380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die Formulierung wurde auf Testplatten aus Polycarbonat, hergestellt aus einem Polycarbonat aus 4,4'-Dihydroxyphenyl-2,2-propan und Kohlensäure, versprüht. Dann wurden die Testplatten bei 100°C/1 h lang getempert, 2 h bei 24°C im Metallisierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine Metallschicht. Anschließend wurde noch 1 h bei 100°C getempert.The formulation was sprayed onto polycarbonate test panels made from a polycarbonate of 4,4'-dihydroxyphenyl-2,2-propane and carbonic acid. Then the test plates were annealed at 100 ° C. for 1 hour, metallized for 2 hours at 24 ° C. in a metallization bath and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 100 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 12 N/25 mm.Adhesive strength according to DIN 53 494: 12 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte wie in Beispiel 8. Als Substrat diente ein Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure.The spray activator formulation was prepared as in Example 8. A blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid served as the substrate.
Nach Versprühen der Formulierung auf Testplatten, wurde bei 70°C/1 h lang getempert, dann 2 h lang bei 24°C im Metallisierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine zusammenhängende Metallschicht. Anschließend wurde noch 1 h bei 70°C getempert.After spraying the formulation on test plates, the mixture was annealed at 70 ° C. for 1 hour, then at 24 ° C. for 2 hours Metallization bath metallized and rinsed thoroughly with water. A coherent metal layer was obtained. The mixture was then heated at 70 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 14 N/25 mm.Adhesive strength according to DIN 53 494: 14 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2 g
- Bisacetonitrilpalladiumdichlorid
- 330 ml
- MPA
- 350 ml
- MEK
- 350 ml
- Diacetonalkohol
- 15 g
- Aerosil®380 (380 m²/g nach BET)
- 75 g
- Polyurethan
- 2 g
- Bisacetonitrile palladium dichloride
- 330 ml
- MPA
- 350 ml
- MEK
- 350 ml
- Diacetone alcohol
- 15 g
- Aerosil®380 (380 m² / g according to BET)
- 75 g
- Polyurethane
Die Formulierung wurde auf Testplatten aus Polycarbonat, hergestellt aus einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure, versprüht. Die Platten wurden dann bei 100°C/1 h lang getempert, 2 h bei 24°C im Metallisierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine Metallschicht. Anschließend wurde noch 1 h bei 100°C getempert.The formulation was sprayed onto polycarbonate test panels made from a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid. The plates were then annealed at 100 ° C. for 1 hour, metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 100 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 13 N/25 mmAdhesive strength according to DIN 53 494: 13 N / 25 mm
Die Herstellung der Sprühaktivatorformulierung erfolgte wie in Beispiel 10.The spray activator formulation was prepared as in Example 10.
Als Substrat diente ein Polymerblend wie in Beispiel 9. Nach Versprühen der Formulierung auf Testplatten wurde bei 70°C/1 h lang getempert, dann 2 h lang bei 24°C im Metallierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine Metallschicht. Anschließend wurde 1 h lang bei 70°C getempert.A polymer blend as in Example 9 was used as the substrate. After spraying the formulation onto test plates, the mixture was annealed at 70 ° C. for 1 hour, then metallized at 24 ° C. for 2 hours in a metal plating bath and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 70 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 12 N/25 mm.Adhesive strength according to DIN 53 494: 12 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2,2 g
- Bisacetonitrilpalladiumdichlorid
- 185 ml
- MPA
- 175 ml
- MEK
- 175 ml
- 2-Butoxyethanol
- 15 g
- Aerosil®380 (380 m²/g nach BET)
- 37 g
- Polyurethan
- 2.2 g
- Bisacetonitrile palladium dichloride
- 185 ml
- MPA
- 175 ml
- MEK
- 175 ml
- 2-butoxyethanol
- 15 g
- Aerosil®380 (380 m² / g according to BET)
- 37 g
- Polyurethane
Calciumcarbonat wurde der Formulierung zuletzt zugesetzt, kann aber auch an anderer Stelle bei der Herstellung der Formulierung zugesetzt werden.Calcium carbonate was last added to the formulation, but can also be added elsewhere in the formulation preparation.
Die Formulierung wurde auf Testplatten aus Polycarbonat wie in Beispiel 8 versprüht. Dann wurden die Platten bei 100°C 1 h lang getempert, 2 h bei 24°C in einem Kupferbad metallisiert und mit Wasser gründlich gespült.The formulation was sprayed onto polycarbonate test panels as in Example 8. The plates were then annealed at 100 ° C. for 1 hour, metallized in a copper bath at 24 ° C. for 2 hours and rinsed thoroughly with water.
Man erhielt eine Metallschicht. Anschließend wurde noch 1 h bei 100°C getempert.A metal layer was obtained. The mixture was then heated at 100 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 10 N/25 mm.Adhesive strength according to DIN 53 494: 10 N / 25 mm.
Die Herstellung der Sprühaktivatorformulierung erfolgte wie in Beispiel 12.The spray activator formulation was prepared as in Example 12.
Als Substrat diente ein Blend aus ABS-Polymerisat und einem Polyester wie in Beispiel 9.A blend of ABS polymer and a polyester as in Example 9 was used as the substrate.
Nach Versprühen der Formulierung auf Testplatten, wurde wie 70°C 1 h lang getempert, dann 2 h lang bei 24°C im Metallisierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine Metallschicht. Anschließend wurde noch 1 h bei 70°C getempert.After the formulation had been sprayed onto test plates, the mixture was annealed at 70 ° C. for 1 hour, then metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 70 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 7 N/25 mmAdhesive strength according to DIN 53 494: 7 N / 25 mm
Die Herstellung der Sprühaktivatorformulierung erfolgte aus folgenden Komponenten:
- 2,2 g
- Bisacetonitrilpalladiumdichlorid
- 185 ml
- MPA
- 175 ml
- MEK
- 175 ml
- Diacetonalkohol
- 15 g
- Aerosil®380 (380 m²/g nach BET)
- 37 g
- Polyurethan
- 2.2 g
- Bisacetonitrile palladium dichloride
- 185 ml
- MPA
- 175 ml
- MEK
- 175 ml
- Diacetone alcohol
- 15 g
- Aerosil®380 (380 m² / g according to BET)
- 37 g
- Polyurethane
Calciumcarbonat wurde der Formulierung zuletzt zugesetzt, kann aber auch an anderer Stelle bei der Herstellung der Formulierung zugesetzt werden.Calcium carbonate was last added to the formulation, but can also be added elsewhere in the preparation of the formulation.
Die Formulierung wurde auf Testplatten aus Polycarbonat wie in Beispiel 8 versprüht. Dann wurde bei 100°C 1 h lang getempert, 2 h bei 24°C im Metallisierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine Metallschicht. Anschließend wurde noch 1 h lang bei 100°C getempert.The formulation was sprayed onto polycarbonate test panels as in Example 8. The mixture was then heated at 100 ° C. for 1 hour, metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 100 ° C for 1 h.
Haftfestigkeit nach DIN 53 494: 10 N/25 mmAdhesive strength according to DIN 53 494: 10 N / 25 mm
Die Herstellung der Sprühaktivatorformulierung erfolgte wie in Beispiel 14.The spray activator formulation was prepared as in Example 14.
Als Substrat diente eine Blend aus ABS-Polymerisat und einem Polyester wie in Beispiel 9.A blend of ABS polymer and a polyester as in Example 9 was used as the substrate.
Nach Versprühen der Formulierung auf Testplatten wurde bei 70°C 1 h lang getempert, dann 2 h lang bei 24°C im Metallisierungsbad metallisiert und mit Wasser gründlich gespült. Man erhielt eine Metallschicht Anschließend wurde noch 1 h lang bei 70°C getempert.After the formulation had been sprayed onto test plates, the mixture was annealed at 70 ° C. for 1 hour, then metallized in a metallization bath at 24 ° C. for 2 hours and rinsed thoroughly with water. A metal layer was obtained. The mixture was then heated at 70 ° C. for 1 hour.
Haftfestigkeit nach DIN 53 494: 14 N/25 mm.Adhesive strength according to DIN 53 494: 14 N / 25 mm.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4015717 | 1990-05-16 | ||
| DE4015717A DE4015717A1 (en) | 1990-05-16 | 1990-05-16 | FORMULATION FOR ACTIVATING SUBSTRATE SURFACES FOR THEIR CURRENT METALIZATION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0456908A1 true EP0456908A1 (en) | 1991-11-21 |
Family
ID=6406537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90125208A Withdrawn EP0456908A1 (en) | 1990-05-16 | 1990-12-21 | Process for activating substrate surfaces for electroless plating |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5176743A (en) |
| EP (1) | EP0456908A1 (en) |
| JP (1) | JPH04231476A (en) |
| DE (1) | DE4015717A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0562393A1 (en) * | 1992-03-25 | 1993-09-29 | Bayer Ag | Process for improving the adhesion of electrolessly deposited metal coatings |
| DE102008056741A1 (en) | 2008-11-11 | 2010-05-12 | Mtu Aero Engines Gmbh | Wear protection layer for Tial |
| CN104113989A (en) * | 2013-04-17 | 2014-10-22 | 深南电路有限公司 | Method for electrolessly plating a PCB with copper |
| WO2014161523A3 (en) * | 2013-04-04 | 2014-12-24 | Mtu Aero Engines Gmbh | Smoothing method for surfaces of components produced by additive manufacturing |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411795A (en) * | 1992-10-14 | 1995-05-02 | Monsanto Company | Electroless deposition of metal employing thermally stable carrier polymers |
| US5348574A (en) * | 1993-07-02 | 1994-09-20 | Monsanto Company | Metal-coated polyimide |
| DE602006012798D1 (en) * | 2005-01-21 | 2010-04-22 | Commw Scient Ind Res Org | ACTIVATION PROCEDURE USING A MODIFYING AGENT |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0256395B1 (en) * | 1986-08-12 | 1992-07-01 | Bayer Ag | Process for improving the adhesion of electroless metal layers on plastic surfaces |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3560257A (en) * | 1967-01-03 | 1971-02-02 | Kollmorgen Photocircuits | Metallization of insulating substrates |
| US3900320A (en) * | 1971-09-30 | 1975-08-19 | Bell & Howell Co | Activation method for electroless plating |
-
1990
- 1990-05-16 DE DE4015717A patent/DE4015717A1/en not_active Withdrawn
- 1990-12-21 EP EP90125208A patent/EP0456908A1/en not_active Withdrawn
-
1991
- 1991-05-06 US US07/696,431 patent/US5176743A/en not_active Expired - Fee Related
- 1991-05-09 JP JP3132164A patent/JPH04231476A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0256395B1 (en) * | 1986-08-12 | 1992-07-01 | Bayer Ag | Process for improving the adhesion of electroless metal layers on plastic surfaces |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0562393A1 (en) * | 1992-03-25 | 1993-09-29 | Bayer Ag | Process for improving the adhesion of electrolessly deposited metal coatings |
| US5436034A (en) * | 1992-03-25 | 1995-07-25 | Bayer Aktiengesellschaft | Process for improving the adhesiveness of electrolessly deposited metal films |
| DE102008056741A1 (en) | 2008-11-11 | 2010-05-12 | Mtu Aero Engines Gmbh | Wear protection layer for Tial |
| WO2014161523A3 (en) * | 2013-04-04 | 2014-12-24 | Mtu Aero Engines Gmbh | Smoothing method for surfaces of components produced by additive manufacturing |
| CN104113989A (en) * | 2013-04-17 | 2014-10-22 | 深南电路有限公司 | Method for electrolessly plating a PCB with copper |
| CN104113989B (en) * | 2013-04-17 | 2017-11-07 | 深南电路股份有限公司 | The method of heavy copper on pcb board |
Also Published As
| Publication number | Publication date |
|---|---|
| US5176743A (en) | 1993-01-05 |
| DE4015717A1 (en) | 1991-11-21 |
| JPH04231476A (en) | 1992-08-20 |
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